Hydrocarbon-substituted silyl methane compounds



Patented Dec. 20, 1949 HYDBOCARBON-SUBSTITUTED SILYL METHANE COMPOUNDS Robert 0. Saner, Schenectady, N. Y.,asslgnor to General Electric Company, a corporation of NewYork No Drawing. APl lic Serial This invention is concerned with novel compounds of silicon. More particularly, the invention relates to new hydrocarbon-substituted silyl methane compounds corresponding to the general formula OH; CH: X-Ai-CHai-X Hi H:

where X is the same and is a member selected from the class consisting of halogens and the hydroxyl radical. Examples of halogens, which X in the above formula may be are. for instance, chlorine, fluorine, bromine, etc.

The compounds of this invention have utility as intermediates in thepreparation of other chemical compounds or polymers. They are particularly useful in the preparation. of higher molecular weight liquid polymeric materials which may be used for lubricating purposes. These latter higher molecular weight liquid compositions may be further modified with hydrocarbon-substituted polysiloxanes in the presence of suitable agents to yield elastic or resinous products. The products of hydrolysis of the aforementioned halogeno derivatives are useful for preventing flotation of pigment in pigmented resinous coating compositions as is disclosed and claimed in Sage application, Serial No. 794,443, filed December 29, 1947, and assigned to the same assignee as the present invention.

Various methods may be employed for preparing the claimed novel compositions of matter. One method for preparing the claimed halogenterminated silyl methanes comprises heating under pressure at elevated temperatures a trimethylhalogenosilane in the presence of a Friedel-Crafts type catalyst, for instance, aluminum chloride. The particular trimethylhalogenosilane employed will depend on the specific terminal halogen desired to be present on each ation January 22, 1948, No. 3.836

.4 Claims. (01. 260-4483) of matter may be prepared, the following examples are given by way of illustration.

Example 1 To an Aminco steel hydrogenation bomb was I charged 855 grams trimethylchlorosilane and about 23 grams anhydrous aluminum chloride. The bomb was closed and the mixture heated at 375 C. and 1200 p. s. i. for '1 hours. After cooling the bomb, the liquid contents were fractionally distilled to yield a fraction comprising essentially pure bis-(dimethylchlorosilyl) methane boiling at about 178-17? C. at 754 mm. Analysis of the compound showed it to contain 35.55 per cent chlorine (calculated 35.25 per cent).

Into a 1-liter, 3-necked flask equipped with a stirrer, dropping funnel, and double condenser were placed 23 grams magnesium, 50 cc. dry

25 ether, a crystal of iodine, and a few drops of silicon atom in the silyl methane compound.

By fractional distillation it is possible to isolate the desired compound. Another method for making the halogen-terminated silyl methanes ethyl iodide. A solution of 1'79 grams monochloromethyl pentamethyldisiloxane (prepared in accordance with the directions given by Krieble 'et al in J. A. C. S. 6'7, 1810) in 300 cc. dry ether was then added slowly to the magnesium mixture over a 2-hour period. The mixture was then heated under reflux for 30 minutes to complete the formation of the Grlgnard reagent corresponding to the formula (CH3):- SiOSi(CH3) zcHzMgCl. This Grignard reagent was then added during a 1 hour period to a solution of 242 cc. (2.0 mols) of dimethyldichlorosilane in 250 cc. dry ether and the mixture heated under reflux for about 15 minutes. The total reaction mass was then poured carefully over cracked ice and water, the ether layer removed, and all volatile material boiling up to 110 C. was removed by distillation leaving behind 200 grams of a liquid mixture of complex methylsiloxanes comprising [(CHa) 3SiOSi(CHa) 2CHaSi(CHa) 2120 About grams of the above-prepared liquid mixture of complex siloxanes was added slowly to 500 cc. concentrated sulfuric acid to give a homogeneous solution. After cooling the solution, 117 grams (1.5 mols) calcium fluoride was added slowly to the acid solution. The organic material was extracted with 200 cc. n-pentane, and the mixture was fractionally distilled through a Vigreux column to yield about 43 grams bis- (fluorodimethylsilyl)methane having a boiling point of 114-116 C. at atmospheric pressure. This compound had the following properties:

n 1.3780 (14 0.920 Molar refractivity 42.2 (calculated 42.7)

Analysis of the compound showed it to contain 22.1 per cent fluorine (calculated 22.6).

Example 3 Found Calculated Per cent carbon 36.75 36.55 Per cent hydrogen 9.70 9.81

It will be apparent to those skilled in the art that the other compounds embraced by the formula disclosed in thefirst paragraph of the description of the invention, for example, bis-(bromodimethylsilyl) methane, etc., may be prepared using the method described in either Examples 1 or 2.

What I claim as new and desire to secure by Letters Patent of the United States is:

. 1. Chemical compounds corresponding to the general formula,

CH: CHI

xl-CHP' 1-1! where X is the same and is a member selected from the class consisting of halogens and the hydroxyl radical.

2. Bis (dimethylchlorosilyl)methane sponding to the formula cm on;

a H: 3. Bis (dlmethylfluorosilyl)methane sponding to the formula corre- F- l-CHr- 1-1 4. Bis (dimethylhydroxysilyl)methane corresponding to the formula ROBERT O. SAUER.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Name Date Patnode Aug. '7, 1945 OTHER REFERENCES Goodwin J. A. C. 8.," vol. 69 (1947) pa e 2247. Sommer "J. A. C.'S.,. vol. 69 (1947), page 980.

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